To meet the 2050 EU decarbonization goals, there is a need for new and innovative ideas to increase energy efficiency, which includes reducing the energy consumption of buildings and increasing the use of on-site renewable energy sources. One possible solution for achieving efficient thermal energy transition in the building sector is to assign new functionalities to the building envelope. The building envelope can function as a thermal energy storage system, which can help compensate for irregularities in solar energy availability. This can be accomplished by utilizing phase change materials as the energy storage medium in the building envelope. In this paper, two phase change materials with different melting temperatures of 21 °C and 28 °C are compared for their application in a dynamic solar building envelope. Both experimental and numerical studies were conducted within the scope of this study. The laboratory testing involved simulating the conditions of the four seasons through steady-state and dynamic experiments. The performance of the phase change materials was evaluated using a small-scale PASLINK test stand that imitates indoor and outdoor conditions. A numerical model of a small-scale building envelope was created using data from laboratory tests. The purpose of this model was to investigate how the tested phase change materials perform under different climate conditions. The experimental findings show that RT21HC is better at storing thermal energy in the PCM and releasing it into the indoor area than RT28HC. On the other hand, the numerical simulation results demonstrate that RT28HC has an advantage in terms of thermal storage capacity in climates found in Southern Europe, as it prevents overheating of the room.